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Munoz-Castro A.,Andres Bello University | Munoz-Castro A.,Autonomous University of Chile
Physical Chemistry Chemical Physics | Year: 2014

Application of the planar superatom model to describe the electronic structure, and to gain insights into the stabilization of metal macrocycles supporting closed-shell d10-d10 interactions, is studied through analysis of the membered ring composed by Hg(ii) atoms, namely, [Hg(C(CF3)2)]5. Its electronic structure resembles the level sequence given for a planar jellium model, revealing an electronic configuration given by 1s2 1p4x,y 1d4xy,x2-y2. The analysis of the population of each level of the Hg5core, denotes a slight net bonding into the [Hg(C(CF3)2)]5 ring. However, stabilization is mainly supported by the balance given by a similar population of the jellium levels, which is suggested to be a different scheme for stabilizing d 10 macrocyclic clusters with metallophilic interactions, in the category of long d10-d10 contacts. The extension of the planar jellium model to the relativistic case, including spin-orbit coupling considering the D5h* point group, denotes the consequent splitting for levels with ≠ 0, namely, 1px,y and 1dxy,x 2-y2. In this framework, the electronic configuration is given by 1s1/22 1p3/22 1p 1/22 1d5/22 1d3/2 2, which contribute to the analysis of the electronic structure of planar clusters in terms of spin-orbit coupling, involving molecular spinors (j = ± s) instead of molecular orbitals (pure). This journal is © the Partner Organisations 2014. Source


Munoz-Castro A.,Autonomous University of Chile
Chemical Physics Letters | Year: 2016

The fused-to-single-ring transition is studied through a 10πe series given the series from naphthalene to [10]annulene. Our results suggest that change occurs at certain structure instead of a gradual transition. In the transition point, given by bicyclo[7.1.0]decapentaene, similar magnetic behavior in comparison to the single ring counterpart is found. The systems can be considered to behave as a whole single aromatic structure where the fused counterparts can be treated as a modification in the aromatic path of a single ring aromatic motif, which can viewed as a useful approach to evaluate the formation of defects or larger-rings in graphene motifs. © 2016 Elsevier B.V. All rights reserved. Source


Munoz-Castro A.,Autonomous University of Chile
Chemical Science | Year: 2014

The electronic and structural properties of [Au6{Ni3(CO)6}4]2- pave the way to describe a superatom analogue of the most simple and archetypical hydrocarbon, CH4. In this sense, our interest relies on the plausibility of finding superatomic clusters as analogues for archetypical molecules in organic chemistry, preserving relevant concepts of chemical significance, such as the hybridization of atomic orbitals. In [Au6{Ni3(CO)6}4]2-, a central Au6 core exhibits the formation of superatomic SP3 hybridized orbitals in order to account for the molecular shape and bonding. Inspired by this finding, several clusters were proposed exploring the capabilities of the metallic core to exhibit SP2 and SP superatomic hybrid orbitals. In addition, we include the evaluation of superatomic bonding involving SP3SP3, SP2SP2 and SPSP hybridized cores, which denote single, double and triple superatomic bonds. Our results describe the extension of the localized Lewis structure model to the understanding of clusters according to the superatom model, contributing to the tremendous opportunities for the design of functional clusters and nanoparticles. This journal is © the Partner Organisations 2014. Source


Rauhalahti M.,University of Helsinki | Munoz-Castro A.,Autonomous University of Chile
RSC Advances | Year: 2015

[Sn@Cu12@Sn20]12- represents an archetypal intermetalloid structure composed of several concentric polyhedral shells displaying a highly spherical shape. This feature paves the way to understanding the electronic structure of multilayered structures in terms of interacting superatomic shells. As a result, [Sn@Cu12@Sn20]12- can be regarded formally as [{Sn@Cu12}4-@{Sn20}8-], which ensures a favorable electronic configuration with a sizable HOMO-LUMO gap for the inner core [Sn@Cu12]4-. The interaction between the [Sn@Cu12]4- and [Sn20]8- layers involves a concentric bonding interaction of s-, p- and d-type. The approach employed here is suggested and demonstrated to be a useful strategy for rationalizing multilayer endohedral clusters, which can be extended to nanoparticles or even to less symmetrical systems. © The Royal Society of Chemistry 2015. Source


Munoz-Castro A.,Autonomous University of Chile
Chemical Communications | Year: 2015

The magnetic response of C60 has been studied and compared to its spherical aromatic counterpart C6010+, focusing on the overall and local shielding tensors. A high axis dependence behavior at the outside region of the structure is characterized, unravelling a characteristic pattern of the local chemical shift anisotropy as a consequence of the spherical aromatic behavior. © 2015 The Royal Society of Chemistry. Source

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